Geochemistry of unsaturated soil systems: Aqueous speciation and solubility of minerals and gases in capillary solutions

Lassin, Arnault; Azaroual, Mohamed; Mercury, Lionel

doi:10.1016/j.gca.2005.05.020

Cited by 33 publications

(51 citation statements)

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“…The thermodynamic properties of superheated solutions make them to behave differently with respect to solids and gases solubilities (e.g. [Zilberbrand, 1999], [Mercury et al, 2003], [Mercury et al, 2004] and [Lassin et al, 2005]), which in turn should affect the resulting mineralogical assemblages.…”

Section: Discussionmentioning

confidence: 99%

“…Secondly, superheating modifies the thermodynamic properties of liquid water and thus its solvent properties with respect to gases and solids ( [Zilberbrand, 1997], [Zilberbrand, 1999], [Mercury and Tardy, 1997a], [Mercury and Tardy, 1997b], [Mercury and Tardy, 2001] and [Mercury et al, 2003]). Therefore, the gas-solid-solution equilibria associated with superheated solutions at low T (soil capillarity; [Mercury et al, 2004], [Lassin et al, 2005] and [Pettenati et al, 2008]) and high T (geothermal or hydrothermal environments, especially associated with ore deposits processes), may be strongly modified.…”

Section: Introductionmentioning

confidence: 99%

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Experimental superheating of water and aqueous solutions

Shmulovich

Mercury

Thiéry

et al. 2009

Geochimica et Cosmochimica Acta

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101

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The metastable superheated solutions are liquids in transitory thermodynamic equilibrium inside the stability domain of their vapor (whatever the temperature is). Some natural contexts should allow the superheating of natural aqueous solutions, like the soil capillarity (low T superheating), certain continental and submarine geysers (high T superheating), or even the water state in very arid environments like the Mars subsurface (low T) or the deep crustal rocks (high T). The present paper reports experimental measurements on the superheating range of aqueous solutions contained in quartz as fluid inclusions (Synthetic Fluid Inclusion Technique, SFIT) and brought to superheating state by isochoric cooling. About 40 samples were synthetized at 0.75 GPa and 530-700 °C with internally-heated autoclaves. Nine hundred and sixty-seven inclusions were studied by micro-thermometry, including measuring the temperatures of homogenization (Th: L + V → L) and vapor bubbles nucleation (Tn: L → L + V). The Th-Tn difference corresponds to the intensity of superheating that the trapped liquid can undergo and can be translated into liquid pressure (existing just before nucleation occurs at Tn) by an equation of state. Pure water (840-935 kg m −3 ), dilute NaOH solutions (0.1 and 0.5 mol kg −1 ), NaCl, CaCl 2 and CsCl solutions (1 and 5 mol kg −1 ) demonstrated a surprising ability to undergo tensile stress. The highest tension ever recorded to the best of our knowledge (−146 MPa, 100 °C) is attained in a 5 m CaCl 2 inclusion trapped in quartz matrix, while CsCl solutions qualitatively show still better superheating efficiency. These observations are discussed with regards to the quality of the inner surface of inclusion surfaces (high P-T synthesis conditions) and to the intrinsic cohesion of liquids (thermodynamic and kinetic spinodal). This study demonstrates that natural solutions can reach high levels of superheating, that are accompanied by strong changes of their physicochemical properties.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Experimental superheating of water and aqueous solutions

Shmulovich

Mercury

Thiéry

et al. 2009

Geochimica et Cosmochimica Acta

Self Cite

101

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“…The chemical behaviour of capillary systems has been studied for almost 20 years (Mercury and Tardy, 1997a, b;Zilberbrand, 1999) and the theoretical framework is now well established for calculating the standard thermodynamic properties of chemical compounds submitted to capillary pressure (Mercury and Tardy, 2001;Mercury et al, 2003;Lassin et al, 2005Lassin et al, , 2014. In particular, capillary constraints are imposed on the system according to the Lassin et al (2005) relationship for describing the equilibrium between vapour and capillary aqueous solution, namely:…”

Section: Thermodynamics Of Chemical Reactivity In Capillary Systemsmentioning

confidence: 99%

“…In particular, capillary constraints are imposed on the system according to the Lassin et al (2005) relationship for describing the equilibrium between vapour and capillary aqueous solution, namely:…”

Section: Thermodynamics Of Chemical Reactivity In Capillary Systemsmentioning

confidence: 99%

“…These capillary pressure effects can be taken into account by applying the HKF equations (Helgeson et al, 1981;Tanger and Helgeson, 1988) for calculating the standard partial molar thermodynamic properties of aqueous species, as done by Mercury et al (2003) and Lassin et al (2005Lassin et al ( , 2014. The pressure dependence of the Gibbs energy ‫ܩ∆‬ ሺܶ, ܲሻ of an aqueous complexation reaction can thus be written as follows, considering for example the bicarbonate formation by combination of aqueous ‫ܱܥ‬ ଶ with water:…”

Section: Thermodynamics Of Chemical Reactivity In Capillary Systemsmentioning

confidence: 99%

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Equilibrium partial pressure of CO2 in Callovian–Oxfordian argillite as a function of relative humidity: Experiments and modelling

Lassin

Marty

Gailhanou

et al. 2016

Geochimica et Cosmochimica Acta

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, et al.. Equilibrium partial pressure of CO 2 in Callovian-Oxfordian argillite as a func-tion of relative humidity: experiments and modelling. Geochimica et Cosmochimica Acta, Elsevier, 2016Elsevier, , 186, pp.91-104. 10.1016Elsevier, /j.gca.2016 Accepted Manuscript This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractHaving previously demonstrated that the mineral assemblage of claystone can impose its pCO 2 under saturated conditions, we here study the effect of rock desaturation, i.e.the evaporation of pore water, on the partial pressure of CO 2 (pCO 2 ) in CallovianOxfordian argillite from the Paris Basin (France). In this new study, which combines experiments at room temperature and geochemical modelling, we examine the primary role of capillary forces on chemical equilibria for relative humidity values ranging between 50% and 100%. In particular we are able, without any fitting parameters, to model the experimental decrease of pCO 2 as a function of decreasing water content in the argillite. This application to a complex natural system not only confirms the theoretical concepts of geochemistry in capillary contexts, but is promising with respect to other systems, both natural (soil, rock) and industrial (ceramics, granular material).

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Thermodynamics and Salt Crystallization Kinetics

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2024

Salt Crystallization in Porous Media

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Geochemistry of unsaturated soil systems: Aqueous speciation and solubility of minerals and gases in capillary solutions

Cited by 33 publications

References 49 publications

Experimental superheating of water and aqueous solutions

Experimental superheating of water and aqueous solutions

Equilibrium partial pressure of CO2 in Callovian–Oxfordian argillite as a function of relative humidity: Experiments and modelling

Thermodynamics and Salt Crystallization Kinetics

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